Textile treating compounds and method of applying them to textiles



Patented May 5, 1953 TEXTILE TREATING COMPOUNDS AND METHOD OF APP TEXTILES LYING THEM -TO John Robert Janes, Garden City, N. Y., assignor to Deering Milliken Research Trust, Green- 'wich, Conn., a nonprofit trust of Maine No Drawing. Application September 2, 1948,

Serial No. 47,549

7 Claims. 1

This invention relates to textile finishing com,- pounds, to a process of treating cellulosic, proteinaceous and other textile materials in order to improve their properties, and to the improved cellulosic, proteinaceous and other textile materials thereby produced.

Cellulosic and like textile materials have heretofore been rendered water repellent by treating them with alkyl silicon halides. These compounds are said to react with hydroxyl groups at the surface of the textile, forming a chemical bond therewith and splitting out hydrogen halide. Because 'of the presence of hydrogen halide, however, considerable care must be exercised in carrying ,out theprocess to avoid weakening the cellul'osi'c fabric or otherwise damaging it; It is necessary, for example, to apply the silicon halide at a low temperature under a vacuum or other conditions adapted to carry off hydrogen halide as it is formed. Because of the inconence of atmospheric moisture to form silica polymers and hydrogen halides, and thus must be applied in the absence of moisture; 'Aqueous solutions cannot of course be used, The lower members of the series are corrosive, highly volatile,

low boiling liquids, not pleasant to work with in a textile mill.

Now, in accordance with this invention. cellulosic proteinaceous and other textile materials are treated with quaternary ammonium salt d erivatives of alkyl alkoxy silicon compounds. These compounds improve the water repellency and/or.

softness, dimensional stabilization, flame resistance and crease resistance of the textiles treated therewith. These improved properties may result from reaction of the compoundsof .the in-e vention with the textile material, either at the "silicon-oxygen linkage or at the quaternary am monium group or both, possibly forming cross withstand ordinary laundering and dry cleaning procedures.

the improved properties are ,permanent, and.99

. chloroph y "p entachloropheny fi y Cylohexyl, W010 wpentyl, chloromethyl, chl r pr py l. fi p ny i THE COMPOUNDS OF THE INVENTION They are characterized by the formula:

where: n is an integer from 1 to 3.

R is a saturated or unsaturated, substituted or unsubstituted, aliphatic, aromatic or cycloaliphatic group, or an linkage, where y is an integer from 1 to about 20. The R radicals, if more than one, may be the same or difierent.

Y is bivalent or trivalent organic radical which may be an aliphatic, aromatic or cycloaliphatic hydrocarbon radical of 1 to about 30 carbon atoms or a radical containing a linkage selected from the group consisting of ester, ether, amide, carbamate, and urea linkages, such as COO,

O, CONR, OCONR', NR'CONR', CONR'CONR', OCHzNR'CONR', OCONR'CONR', where R is hydrogen or alkyl. Y may, for example, be methylene, ethylene, propylene, phenylene, decylene, octadecylene, montanylene, butylene, cyclohexylene, or naphthylene, with or without the linkages mentioned N(tert) is the residue of a tertiary amine.

Typical tertiary amine residues include those in which three nitrogen valences are taken up in one ring, as in pyridine, pyrazine, pyrimidine, quinoline, isoquinoline, acridine, and phenanthridene, those in which two nitrogen valences pentyl, and hexy, whether n, secondary or tertiary. B may, for example, be methyl, ethyl, propyl, hexyl, decyl, octadecyl, phenyl, tolyl, dichlorophenyl, trichlorophenyl,

octenyl, or oleyl. X is an anion.

\ When R represents an The general reaction, however, involves action of the corresponding alcohol, its chloromethyl ether, or quaternary ammonium salt on the halogeno silane (Ann. Chim. Phys. (4) 9, 5 (1866); Ann. 488, 56 (1931); and J. Am. Chem. Soc. 68, 70 (1946):

Similarly, a hydroxy amide, urea, ester, carbamate or hydroxy hydrocarbon halide may be used, or their ch-loromethyl ethers or quaternary ammonium salts:

These compounds are white or pale-colored solids, or viscous liquids, soluble or dispersible in water, pyridine, dioxane, xylene, mesityl oxide, benzene, chloroform, ethyl alcohol, carbon, tetrachloride, ethylene dichloride, ether and acetone.

The quaternary ammonium group of these compounds is decomposed by heating the dry compound above about 90 C., liberating the tertiary amine and a radical of the form It may also be hydrolyzed by water at temperatures as low as to C., forming these products.

In considering the possible reactions that may follow decomposition of this group, it must be borne in mind that the radical Y also influences the reactions which may occur. Y groups which include urea, amide or carbamate groups, and thus are of the form CONHCH2- are readily polymerized; whether or not the silicon-oxygen linkage is hydrolyzed affect only the type of polymers formed. For example, if the compound contains two quaternary ammonium groups, linear polymers may form even though the silicon-oxygen linkage remain unhydrolyzed.

l HX HCHO N(tert) I N (text) The silicon-oxygen linkage is hydrolys'able, but its ease of hydrolysis depends upon the number of carbon atoms of the R group attached to the silicon atom. Hydrolysis may be inhibited in the presence of a tertiary amine, such as pyridine, trimethylamine, triethylamine, or quinoline. When all of the R groups are less than about 6 carbon atoms, the linkage is hydrolized more or less rapidly by moisture at room temperature, and the hydrolysis is exothermic. If an R group of 6 to about carbons present, the linkage is hydrolyzed at room temperature only by dilute acid or base, the required conditions for hydrolysis thereafter growing more severe as the number of carbons increases, i. e., as the R, groups impart to the compound more of the character of a hydrocarbon. Hydrolysis when an R group C1'1H35 is present may, for example, be accomplished only by warming in dilute acid or base at 40 to 80 0., or by subjecting it to a steam treatment.

Thus, during treatment, apparently two unrelated reactions may occur, and these may proceed concurrently or successively, depending upon the treatment conditions. The free radical liberated by decomposition of the quaternary ammonium group, may polymerize to form a resin, may react with another free radical to form a dimer, or react with water to form a fatty alcohol. If the reaction is brought about in the presence of cellulose, it may react with a hydroxyl group of the cellulose molecule to form an ether of the general structure This ether may also hydrolyze to give the radical O-SiRn and the ether cellulose-OY. The former may react as described below, while the latter may cross-link with another cellulose molecule.

The radicals liberated by hydrolysis of the SiO linkages are of the form RnSi or RmSi[O-] and YN(tert)X. The latter may react as set forth above.

The former may polymerize to form a silicone resin, 9. siloxane, Rn-SlO-si-Rn, or a silanol RnSiOH. If n=2, the resin will probably be a typical linear silicone fluid, while if n=l, cross-linking between silicone chains may occur, and a silicone solid will result. Interest ing polymers are formed when mixtures of compounds are employed in which n is 1, 2 and 3 (i. e., mixtures where n=1 and 2, or 1 and 3, or 2 and 3). The preparation of silicone resins is now well understood, and beyond the scope of this invention. The discussion by Hardy and Megson, Quarterly Reviews, 2, 25 (1948), is of assistance in determining proper ratios of the resin components.

Moreover, the former may also react with a hydroxyl group of the cellulose molecule, yielding an ether of the form cellu1ose-O-SiRn, or possibly, in addition, cross-linkages between cellulose molecules, where n=1 or 2. Also, when n=1 or 2, reaction may occur with two or more hydroxyls of the same cellulose molecule. This cellulose-oxygen linkage is not stable to moisture, where R is an alkyl group of less than 3 carbons; in this case, upon hydrolysis a silicone polymer may be formed as set forth. However, the greater the number of carbon atoms in the R group, the more stable this other bond is; when an B group of ten or more carbon atoms is present, it is quite resistant to hydrolysis, even by acid or base, and even appears to be more resistant to hydrolysis than the siliconoxygen bond of the compounds of the invention.

When the compounds of the invention are ap- 6 plied to cellulosic or proteinaceous materialsand then decomposed, it will be understood that any or all of the above chemical reactions may occur consecutively or simultaneously. Thus, any or all of these cellulose ethers may be formed:

One reaction may occur to the exclusion of the others. Also, additional reactions not yet understood and not set forth may be responsible in whole or in part for the improvement in properties obtained when the compounds of the invention are applied to textiles.

This reaction takes place with cellulosic materials as a class regardless of their physical form, whether fibers, roving, yarns, fabrics or films; typical natural cellulosic materials including cotton, flax, jute, hemp, ramie, linen, sisal, bast and wood pulp. Reaction also occurs with artificial cellulosic films and fibers such as regenerated cellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose acetate propionate and ethyl cellulose. Apparently a similar reaction occurs with the protein molecule; the compounds give similar results with wool, silk, casein, albumen, alginate and like proteinaceous films or fibers, regardless of their stage of manufacture. They are also useful with synthetic fibers, such as nylon (i. e., polyamides) and vinyon (i. e., polyvinyl resins).

When the compounds of the invention are applied to cellulosic or proteinaceous textiles, the properties of the textile are modified depending upon the particular compound employed and the quantity of the compound deposited in or on the material. In general, the more compound employed, the more intense is the degree of improvement observed. Amounts between about 0;025% and about 20% by the dry weight of the treated textile are usually sufiicient. Factors, other than quantity, influencing the modification of properties obtained are listed in the following table. It will be understood that any one or all of the factors listed for a given-property may be utilized to introduce such property into the textile.

Property Influencing Factor n=1 or 2.

R=l to 20 carbon alkyl group or an aromatic or cycloaliphatic group bearing such an alkyl group.

Y=6 to 12 carbons.

n=1, 2, or 3.

R=l to 3 carbon alkyl.

lY=halogen containing 1 group of 1 Y= 10 to 30 carbons.

Water repellency Dimensional stabilization.--

R=1 to 3 carbon alkyl.

Flame resistance Crease resistance 1 The higher the proportion o fhalogen, the better the flame resist-l ance.

7 Other finishing agents: may be: applied tothe textile; as described below.

THE PROCESS. OF THE INVENTION In brief, the textile material is treated with a solution or dispersion of a compound or mixture of compounds of the invention, and then subjected to a treatment adapted to bring about chemical reaction between the. compound and itself and/or the textile molecule, i. e., the protein or the cellulose. Towards this end, the material may be subjected to an acid or alkali. treatment, and/or heated or baked for a time and at a temperature suflicient to cure it. The solvent is wholly or partially removed by heat. and/or in. a vacuum. If desired, curing may be carried out simultaneously with solvent removal or drying. The cured material. may be-washed with acid or. alkali to.- remove. unreacted. material.andlundesirable. byproducts of the reaction.

The conditionsforcarrying out. the impregnation. depend upon the natureof the. material. being treated, the compound and the concentration of, the treating solution, and the. type offindesired. The. compounds are ordinarily employed; in the-form of. anaqueous solution; or. dispersion. If-,, however; the: silicon-oxygen. linkage susceptible to.,-hydrolysis at the treating conditions, substantial amounts ofa. tertiary amine may be; added. For. this purpose pyridine quincline; quinaldine' triethanolamine, and triethylamine. are; suitable-.. If tightly woven fabrics, are to; be. treated itisfrequently advantageous to add. to. the treating. solution a. small; quantity of alcohol, acetone or. a. wet-ting: agent of, the cationic; or. nonionic type, to: assist penetration. Solutions of: the compounds in. organic liquids such as toluene-,benzene; ethyl. alcohol, pyridine; and ethylene dichloride;which-maybe anhydrous if, desired; also, be employed.

The;concentration of the treating solution depends,- upon the material being treated and the result desired. Soft finishes which impart only a small degree of water-repellencyand flame resistance are obtained when the. treating solution contains between about 0.1. and about. 0.5% of the; compound, while highly flame retardant; water repellent, soft finishes: are obtained when theizconcentration is betweena-bout' 0.5 and 'about 20%: compound, dependingjupon the structure of r thecompound-employed. The material may also be rendered: crease resistant and; dimensionally stable by use of treating-solutions ofthese concentrations. These'figuresare basedona 100% pick-up: or treatin solution by weightoi the-ma:- terial being treated. If a lower pick-up i obtained, the concentration of the treating solution shouldbe increased proportionately; This is particularly true, for example, when tightly woven fabrics are beingtreated;

Inorder to revent .orminimize. loss in tensile strengthandtendering when cellulosic materials are treated withthezc-ompounds of the invention, the pH of the treating;solution'should be adjusted so -that-,-thezcured treatedsmaterial has a pH between and 7.5,- preferably- 6 and 7. The pHof the; cured-.material isconsidered as equivalent to that of the watervextract obtained by immersing egramstof-the cured material in 508 cc. of. Water for one-hali hour. In most cases it will be found if the 'pH&Of the'treating solution is between 5 andlO,goodresultswillbe had; Buffers, which preferably are non-volatile at the curing temperature used, and,inert.both to thecompounds of the invention and to the textile mater rial, are employed to maintain the pH of. the treating solution at the desired value. Bases such as triethanolam-ine, dieth'anolamine', sodium acetate, ammonium acetate, pyridine, hexamethylene tetramine, and sodium formate, or acids such as lactic, glycolic or alpha. hyd'roxybutanoic acidsmay be added to adjust the pH- of: the solution.

Other textilev finishing agents may be. added to the treating solution. to: give a fuller or stiffer handle to the material. Substancessuch as ammonium. acetate, carrag-heen. moss, gum tragacanth, natural resins and waxes, ammonium stearate or water-soluble. cellulosederivatives; such as methyl, hydroxyethyl and sodium carboxymethy-l cellulose, may be added Gther water repellent compounds may be added it desired, provided they do not diminishthe efiect of the compounds of theinvention. Cationic quaternary ammonium compounds may be employed, for'example, octadecyloxymethylpyridinium chloride, N,N'-di chloropyridiniummethyl) paraphenylenedi-carba-mate,, stearamidomethylpyridiniumchloride and: hexamethylene or decamethylen'e ditoxymethylpyridinium chloride) Where these additional agents are insoluble in water, they arezfrequently dispersed in the treating; solution by. the quaternary ammonium. compoundsof the invention, which alsolhave detergent-properties.

The treating operation is. preferably carried out at temperatures below 40 C. if the compounds of. the. invention. are readily decomposed. in. aqueous or organic solvent solutions or dispersions; More staole: compoundsv may be applied: at more elevated temperatures, insome-cases-even at the boiling point, but even the most stable compounds tend to hydrolyze when kept at suclitemperatures for any extended period of time, and give aless satisfactory finishnot asresistant to organic.sol vents. In general-,,thereforathetreating operationliscarried out at between 10 and 40? C.-

The treatment. iscarrieda out. by padding; or soaking the. material in the treating: solution. or dispersionx. GonaentionalYZ-or 3 roll-padders may be used. The-material.is-preferably subjectedto pressure: during or after treatment in order to insureithorough'impregnation; Surplusliquor is removed by squeezing. or hydroextracting; When the-textile: material is= being; dimensionally, stabilized and/or. crease proofed, anieifect obtained with: certain of. the: compounds of the invention; ittis themstretchedzWhile still wet to its original dimensions. so: that drying: and: baking may be carried out. while: the material: isunder: tension; This stretching step is unnecessary when the material is .merely, to :be renderedrflame retardant and/or. watererepellenti In thisconnection, it: should: banote'd: that the effects: of: the: treatment. are: not. always entirely fast. to severe; laundering; For: this; reason it; is important. thatv the 1 treatment be appli ed. tol the fabric in its nomnal;.relaredstatai. e.', itsnormal dimensions. If.treatment andicuring;are:carried outtwitlrzan oyer stretchedfabric, thelatter will bestabili'zed atits extendedsiza: When the-.stabilizastionr. effect is: worn off. on: laundering, the fabric will thenishrinkctoitsinormahrelaxed size; On; the:- other: hand, if: the: process iacarried: out omazfa'bric inlits normal dimensions,,thergradual loss. of. finisln during laundering will not, cause shrinkage;

liz'rom this lpointron; the processtfollowed: must take? into: consideration.- the =particulan compound employed: andathe finish. desired; that-is; whether 9 it is desired to decompose the compound at the quaternary ammonium group only, or both it and the silicon-oxygen linkage.

It is not necessary to hydrolyze the siliconoxygen linkage. When it is stable to hydrolys s, permanent water-repellency, softness and flame retardance may be imparted by merely decomposing the quaternary ammonium group in situ on the textile. In this event the impregnated textile is dried at a temperature low enough to inhibit decomposition of the quaternary ammonium group (see later) and then cured. This procedure gives good results with compounds such as octadecyldimethyl(ethoxypyridinium chloride) silane and trimethyl(octadecyloxypryridinium chloride) silane.

When it is desired to hydrolyze the siliconoxygen linkage as well, it is possible by suitable steps first to bring about decomposition of the quaternary ammonium ialide group, and then to hydrolyze the silicon-oxygen linkage. In this procedure, the impregnated textile is dried, cured at a temperature between about 80 and about 200 C., impregnated with a solution adapted to hydrolyze the silicon-oxygen linkage, and then warmed at 40 to 150 C. and cured a second time at temperatures from about 80 to about 250 C. This procedure gives consistently good results with most of the compounds of the invention. It does require two impregnation, drying and two baking steps, however.

Alternatively, both decompositions may be caused to occur simultaneously, or hydrolysis of the silicon-oxygen linkage may be made to occur first.

These procedures are quickerand more economical, since in the latter case the hydrolysis of the silicon-oxygen linkage may be made to occur in the first textile treating bath or directly thereafter, and the subsequent chemical reac' tions carried nearly to completion before thetextile is dried, and then completed during the baking step, at which time decomposition of the quaternary ammonium salt also occurs, while in the former case both decompositions are made to occur during the first curing step. These procedures have the advantage of requiring only one impregnation, drying and curing.

If the impregnated textile material is heated at temperatures above about 100 C. while still wet, premature decomposition of the quaternary ammonium group may occur. It is usually important that this be prevented, since in many instances no permanent effect may thereafter be obtained. In such cases, it is best to first dry the fabric thoroughly so that baking and cur-v ing may be carried out in the absence of moisture. Thick or tightly woven fabrics especially must be dried with care, for they tend to retain moisture for a long period of time, even at elevated temperatures. The drying temperature is preferably between 30 and 80 C., but the temperature of drying is less important than the speed and other conditions. If the fabric is dried in more or less stagnant air, as in an oven without artificial circulation, it should not be submitted to a drying temperature of more than 30 C. When, on the other hand, it is dried in a blast of hot air so that the Water may be removed rapidly, say in about 3 minutes, then the drying temperature may rise to 80 Again, when the treated material is dried on a steam-heated cyl: inder at 120 C'., no permanent effect may be obtained.

The curing or baking temperatures should be between and 260 C. For decomposition of the quaternary ammonium salt, temperatures between 80 and 150 C. are preferred, while ouring of the silicone-containing reaction products may require temperatures up to 50 C. to C. higher; that is, the preferred range in this case lies between 100 and 250 C. The time of baking is inversely proportional to the temperature used, and both depend to some extent on the nature of the compound and of the textile material. A longer baking time and a relatively low temperature should be used with thick or tightly Woven fabrics in order that the heating may be uniform throughout, while open weave fabrics or fabrics of synthetic fibers, such as nylon, may safely be heated at higher temperatures. If tendering of the material is to be avoided, the time of baking is preferably kept as short as possible and the baking temperature as low as possible.

In the case of open weave fabrics, if a brisk circulation of air is provided around and through the material, the preliminary drying step may be omitted and the treated material heated at once at the baking or curing temperature.

The drying operation may be carried out in a covered tenter frame, while curing or baking is best carried out on a loom, mat, roll or air lay dryer.

Hydrolysis of the silicon-oxygen linkage, which is usually accompanied by polymerization and other chemical interaction of the hydrolysis products if n=2 or 1, may be carried out in aqueous neutral, alkaline or acidic media at room or elevated temperatures. It may therefore occur spontaneously in the, initial treating solution. Addition of a substantial amount of a tertiary amine, from 0.5 to 1.5 moles of the amine per mole of the compound, seems to inhibit either the hydrolysis or the subsequent chemical reactions; upon volatilization of the amine in a later heating step, both reactions proceed as though it had never been present. It may also be carried out after impregnation and/or curing while the textile is traveling through a bath of the hydrolysing media, or while the textile is wet with such a medium or its vapors.

Hydrolysis in neutral or alkaline solution favors formation of linear or cage type polymers, while hydrolysis in acidic media favors formation of cyclic silicon compounds. Acid hydrolysis may also be objectionable with cellulosic fabrics because tendering may result. It is desirable that only the stoichiometric amount of water to form the expected polymer be present, but this is not essential, and in fact is a condition almost impossible to attain after the compound has been applied to the textile.

Hydrolysis may be carried out at from, 10 to 100 C., depending upon the ease of hydrolysis, as set forth previously. The reaction may be exothermic. Usually it is complete in 15 minutes to an hour, but it may require up to five hours. Solution pH values between about 5 and about 10 are preferred, but stronger solutions may be used where no fabric damage is caused. Bases such as sodium and ammonium hydroxide and acids such as hydrochloric or sulfuric are suitable.

The chemical reactions subsequent to hydrolysis are expedited by higher temperatures, and should also be conducted in the presence of moisture, and/or an acid or base. Following hydrolysis, and without rinsing, therefore, the

treated textile may be warmed while keeping it i wet, as in a moist atmosphere, at from 40 to 150 C., for from minutes to several hours, and then cured at 80 to 250 C. for a period of a few minutes to several hours. Again, possible damage to the fabric governs the temperature and time employed. The cured fabrics may be washed and/ or rinsed, prior to or after final :curing, to remove acid or base, by products and unreacted material.

Example 1 Dry ethylene oxide gas is bubbled slowly through one mole of trimethylchlorosilane contained in .a three-neck flask fitted with calcium chloride tube, water cooled :reflux condenser and gas inlet tube. Pressure inside the vesselis maintained a few millimeters above atmospheric and the chlorosilane is heated to boiling at the start of the reaction. The reaction is exothermic, vso that no heating is required after react-ion has begun. The reaction is permitted to continue for about two to three hours. The 2-chloroethoxy trimethyl silane is recovered and purified by traction-a1 distillation.

The procedure is repeated using 'trichloromethyl silane, and the trichloroethoxymethyl silane likewise is recovered and purified by fractional distillation.

Pyridinium hydrochloride is prepared by bubbling dry hydrogen chloride gas into a solution of pyridine in dry benzene. The pYrid-inium salt or each of the ethoxy silanes 'is prepared by pouring the silane slowly, with constant stirring, into the pyridinium hydrochloride solution and then warming it at to 80 C. until the quaternary The precipitated The salts Equal parts of each salt, together with an equal weight of pyridine, are dissolved in water to form a ten per cent solution. The pH of the .solution is adjusted -to 8.0 by addition of a small amount of triethanolamine. A cotton twill fabric is padded with the solution at room temperature to a 100% pick-up by weight. The treated fabric is warmed at 60 C. until dry and baked at 120 C. for three minutes. The fabric is then padded with a 0.3 per cent solution of sodium hydroxide, heated at 40 C. During passage, the temperature of the wet cloth rises spontaneously to 60-05 C. Next, the fabric is removed from the padder and allowed to stand at room temperature in a moist atmosphere for two hours. It is then dried and cured by heating at 150 for 1'5 minutes. Finally, the fabric is washed with a soap solution, rinsed and dried. The material is water repellent, and also has good crease-resistance, dimensional stability and shrinkage resistance.

Example 2 One mole of di-( 1,3,5-trichlorop'henyl) dichloro silane is heated to 60 C. in a three-neck, round bottom fiask fitted with caiicum chloride tube, reflux condenser and gas inlet. Ethylene oxide gas is bubbled through the mixture until reaction is complete, which requires about three to six hours. The mixture is distilled and the di-(2- chloroethoxy) dill,3,5-trichlorophenyl) silane recovered.

One mole of the silane is dissolved in 350 cc. of dry benzene together with one mole of pyridine. Dry hydrogen chloride gas is bubbled through this solution while warming .it at C. until formation of the corresponding pyridinium chloride of the formula:

r i g The compound is dissolved in a mixture of equal parts of pyridine and anhydrous ethanol to form an eight per cent solution. A viscose rayon fabric is padded with this solution to a hundred per cent pick-up by weight. The .fabric is then passed through a bath containing 1% sodium hydroxide solution and held at a temperature of 50 C., at a rate such that each section of the cloth remains in the solution for one-half hour. The wet cloth is warmed .at 60 C. for another hour in a moist atmosphere to prevent evaporation. The fabric is dried at 60 C., baked at 150 C. for 15 minutes, and rinsed. The resulting fabric is flame resistant and shows improved water repellency, both of which are permanent to washing.

Example 3 200 parts of ethylene chlorohydrin and 220 parts of dry pyridine are heated together for 24 hours at C., care being taken to exclude moisture. One mole of dimethyl dichloro silane is placed in a 3-liter, 3-necked flask fitted with a dropping funnel, calcium chloride tube and reflux condenser. To this is added, with cooling and over a period of two and one-half hours, the hydroxyethyl pyridinium chloride solution. The mixture is warmed at 60 until evolution of hydrogen chloride ceases, andthen subjected to a vacuum to remove hydrogen chloride and excess pyridine, together with unrea'cted silane, and the pyridinium salt recovered. This salt has the formula:

This procedure is repeated using trimethylchlorosilane.

' One part of trimethyl '(ethoxy pyr'idinium chloride) silane and two parts of dimethyl (diethoXy pyridinium chloride) silane are dissolved in a solution'containing equal parts of pyridine and water, to form a five per cent solution. This solution is padded on a wool fabric to a 100% pick-up by weight. The fabric is dried at 50 C. and then baked at C. for 5 minutes. The cured fabric is immersed in a 0.5% sodium hydroxide solution and traveled slowly through the solution so that each portion of the fabric remains in the solution for one hour. The tern perature of the bath is held at 40 to 50 C. during the treatment. The fabric is then removed from the bath and allowed to remain in a humid oven at a temperature of 00 C. for two hours. The fabric is dried and cured at C. for twenty minutes. The treated fabric has improved dimensional stability and is water repellent.

A nylon fabric treated in the same way and baked at 205 C. for five minutes in the final step likewise has increased water repellency.

Example 4 Propylene oxide is bubbled into a mixture of methyl trichlorosilane and dirnethyl dichlorosilane held at 60 0., according to the procedure set forth in Example 1, until reaction is complete. The solution is then distilled to recover the mixture of propoxy silanes. The silanes are then added to a solution of pyridinium hydrochloride in benzene and the mixture warmed at 50 C. for one hour to form the corresponding pyridinium chlorides of the formulaer These are dissolved in a mixture of equal weights of water and pyridine to form a ten per cent solution. An acetate rayon gabardine fabric is padded with the solution to 100% pick-up weight. The treated fabric is dried at 70 C. and then cured at 140 C. for minutes. The cured fabric is immersed in a bath containing 1.5% aqueous sodium hydroxide, warmed at 50 C., for one hour. It is then warmed in a humid atmosphere in an oven at 60 C. for three additional hours and finally dried and cured at 160 C. for 20 minutes. The resulting fabric is water repellent, crease resistant and dimensionally stable.

Example 5 One mole of w-chloroctadecanol and 250 parts of pyridine are heated together for 24 hours at 100 C., care being taken to exclude moisture. The solution is added dropwise to two moles of trimethylchlorosilane contained in a threenecked, 2-liter flask fitted with reflux condenser, dropping funnel and calcium chloride tube. The flask is kept at a temperature of 50 C. during the reaction and addition of the pyridinium halide continued over a period of three hours. Reaction is continued until evolution of hydrogen chloride ceases. The mixture is then subjected to a vacuum to remove unreacted pyridine and trimethylchlorosilane. The quaternary pyridinium halide is recovered. This compound has the formula:

This compound is dissolved in water to form an eight per cent solution whose pH is adjusted to 8 by addition of triethanolamine. A cotton poplin fabric is padded with this solution to a 100% pick-up by weight. The fabric is dried at 60 C. and then baked at 130 C. for 3 minutes. The cured fabric is immersed in a 5% sodium hydroxide solution which is warmed to 60 C. Passage through the solution is regulated so that the fabric remains therein for one-half hour. The fabric, while still wet, is then warmed at C. for an additional 30 minutes in a moist I atmosphere and then heated rapidly to 150 C. and held at that temperature for 10 minutes. The resulting product is water repellent and shows improved dimensional stability.

Example 6 One mole of octadecyldimethylchlorosilane is placed in a three-neck, two-liter flask fitted with reflux condenser, calcium chloride tube and gas inlet tube. The silane is heated to 50-60 C. and ethylene oxide then bubbled through the mixture until reaction is complete. This may be evidenced by failure of the mixture to gain additional weight. The mixture is then subjected to a vacuum to remove unreacted silane. The octadecyldimethylchloroethoxysilane may be purified by fractional distillation at 2 millimeters pressure.

Pyridinium hydrochloride is prepared by bubbling dry hydrogen chloride into a solution of pyridine in dry benzene. The chloroethoxysilane is added slowly to this solution while warming the latter to 60 and with rapid stirring. The pyridinium halide which forms has the formula:

This compound is dissolved in water to form a 10% solution. A rayon fabric is padded with this solution to a pick-up by weight, dried at 70 C. for one hour and then baked at C. for 5 minutes. After rinsing, a sample of the fabric shows good water repellency. The remainder of the cured fabric is immersed in a bath containing an aqueous 1% solution of sodium hydroxide held at 65 C. and travelled through it at such a rate that a given portion remains in the bath for one-half hour. The fabric is then dried slowly at 80 C. and finally cured at C. for 15 minutes, rinsed and dried. The treated fabric shows a somewhat better water repellency than the other sample, but both portions are satisfactory.

Example 7 One mole of dimethyldichlorosilane is placed in a three-necked two-liter flask fitted with stirrer. reflux condenser, dropping funnel and calcium chloride tube. To this is added dropwise a solution of wor A-hydroxystearamide dissolved in petroleum ether. The reaction mixture is kept at a temperature of 60 C. and heating continued until evolution of hydrogen chloride ceases. To the solution is added one mole of paraformaldehyde. The mixture is heated to 40 C. and dry hydrogen chloride bubbled through the solution until the chloromethyl compound is formed. Water from the reaction is removed as it is formed by a trap afiixed below the reflux condenser. Reaction is complete when no further water is liberated. The solvent and excess hydrogen chloride are removed by subjecting the solu-.- tion to a vacuum and the chloromethyl compound so obtained is added dropwise to an excess of pyridine at 40 C. The precipitate which forms is separated and dried in vacuo. The w-hydrox-y derivative has the formula:

while the x-hydroxy derivative has the formula:

The compound is dissolved in water to form a 6% solution by weight. A cotton fabric is padded with this solution to 100% pick-up by weight, dried at 50 C. and then baked at 110 C. for onehalf hour. The cured fabric is immersed in a. bath containing 1% ammonium hydroxide solution for one and one-half hours. During this period the temperature of the bath rises to 40 C. The treated fabric is then warmed to 60 C. in a moist atmosphere, to prevent loss of water, for an additional hour, and is then dried, and cured at 125 C. for one hour. The product obtained using either compound is permanently water repellent and also shows a high degree of dimensional stabilization.

Example 8 One mole of triethylchlorosilane is placed in a three-necked round bottom flask fitted with mercury-sealed stirrer, calcium chloride tube and dropping funnel. The silane is warmed to 60 C. and to it is added, dropwise, with constant stirring, a solution of monomethylolurea in benzene.

The mixture is heated at this temperature until evolution of hydrogen chloride ceases.

The mercury-sealed stirrer is replaced with a water-cooled reflux condenser. To the reaction mixture is added one mole of paraformaldehyde dispersed in dioxane and dry hydrogen chloride is then bubbled through the mixture. Water which is liberated is separated as it is formed in a trap afiixed below the reflux condenser. Reaction is continued by warming the mixture at 60 C. until evolution of water has ceased. Excess hydrogen chloride gas and solvent are removed by subjecting the mixture to a vacuum and warming at C. The compound which separates is added in small amounts to an excess of pyridine with rapid stirring, and the resulting mixture warmed gently at C. for a. short period. The pyridinium chloride, of the formula is recovered and dried in vacuo.

This procedure is repeated with dimethyldichlorosilane in place of triethylchlorosilane, and the analogous salt obtained.

Both compounds, in the ratio of one part of the former to two parts of the latter, are then dissolved in a solution containing equal weights of water and pyridine to form a 10% solution by weight. Cotton, wool and rayon fabrics are individually padded with this solution at room temperature to a 100% pick-up by weight and dried at 60 C. The dry fabrics are heated at 125 C. for ten minutes and divided into two portions. One portion is passed slowly through a bath heated to 50 C. and containing aqueous 2% sodium hydroxide solution. The travel time of the cloths through the bath is one hour. The other portion of the cloths is passed through a bath heated to 40 C. containing 2% hydrogen chloride solution. All the cloths are held at 60 C. in a moist atmosphere fOr one hour, and then 16 baked at 150 C. for 20 minutes, and rinsed. The products show a high degree of permanent water repellency, crease-resistance and dimensional stability.

Example 9 Dimethyldi(oxylaurylcarbamylmethylene pyridinium chloride) silane, of the formula:

is prepared using the procedure of Example 7, w-hydroxylauryl carbamate being employed instead of w-hydroxystearamide. This compound is dissolved in water to form an 8% solution by weight. A rayon-cotton gabardine fabric is padded with this solution to a pick-up, dried at 80 C., and then baked at C. for 5 minutes. The cured fabric is padded with a 2% sodium hydroxide solution at 60 0., allowing it to remain in the bath for 20 minutes, and then warmed, while still wet, at 60 C. for two hours and cured at 160 C. for 15 minutes. The resulting fabric is permanently water repellent.

Example 10 To one mole of 1,10-decamethyleneg1ycol in a three-necked, two-liter, round bottom flask fitted with mercury-sealed stirrer, calcium chloride tube and dropping funnel, is added, dropwise, over a three-hour period, one mole of dimethyloctadecylchlorosilane. Reaction is continued at 60 C. until evolution of hydrogen chloride ceases. Excess hydrogen chloride is then removed in a vacuum, the reaction mixture is dissolved in benzene, and one mole of paraformaldehyde added. The stirrer is replaced with water reflux condenser and the dropping funnel with a gas inlet tube. Dry hydrogen chloride gas is bubbled through the mixture, which is heated to reflux, until the solution becomes clear. Water which forms in the course of the reaction is removed by a trap afiixed below the reflux condenser. The mixture is then subjected to a vacuum to remove benzene and excess paraiormaldehyde and hydrogen chloride. The product is added in small amounts to an excess of pyridine, and the mixture warmed until the pyridinium chloride separates. This is filtered and. dried in vacuo. This compound has the formula:

A sufficient quantity of the compound is dissolved in a mixture of equal weights of pyridine and water to form a 5% solution, which is then applied to a rayon fabric. The fabric is dried at 50 C. and cured at 110 C. It is then passed slowly through a bath held at 75 C. and containing an aqueous 2.5% sodium hydroxide solution, so that the travel time is one hour. The cloth is squeezed to a 100% pick-up and then rinsed and finally baked in a humid atmosphere or with steam. at 100 C. for one hour and at C. for 15 minutes. The cured cloth is rinsed and dried. The product is permanently water repellent and dimensionally stable.

Example 11 One mole of dioctadecyldichlorosilane is placed in a three-necked flask fitted with mercury- 'dropwise, over a three-hour period, with constant stirring, one mole of hydroxymethyl a-chloro acetate. Heating is continued until evolution of hydrogen chloride ceases. The reaction product is subjected to a vacuum in order to remove hydrogen chloride gas, and is then added slowly, in small quantities, to an excess of pyridine heated to 40 C. The pyridine solution is then warmed to 60 C. until separation of pyridinium halide, which has the formula:

This compound is applied to a cotton fabric using the procedure set forth in Example 10. The treated fabric shows excellent water repellency.

Example 12 Two moles of hydroxy acetamide are added in small portions to 2 moles of trimethylchlorosilane, heated to 60 C. in a three-necked flask fitted with mercury-sealed stirrer, reflux condenser, calcium chloride tube and dropping funnel. Heating is continued until evolution of hydrogen chloride ceases. The product is subjected to a vacuum to remove hydrogen chloride and unreacted chlorosilane.

1.5 moles of the silane is then heated with 0.75 mole of paraiormaldehyde in a vacuum until evolution of water ceases. (See French Patent No. 782,330.) The product is recrystallized from carbon tetrachloride.

One mole of the resulting diamidomethane and one mole of paraformaldehyde are mixed with 300 parts of benzene. The mixture is heated at 60 C. and stirred. Dry hydrogen chloride gas is passed in, until when a test portion is cooled no solid is seen to separate. The mixture is allowed to settle and the benzene solution is removed from the lower aqueous layer. Benzene and hydrogen chloride gas are removed under reduced pressure and the chloromethyl compound recovered. This is added in small amounts to an excess of pyridine. The pyridine is warmed at 60 C. until the pyridinium halide separates. This is filtered off and dried. It has the formula:

This compound is dissolved in a solution containing equal weights of pyridine and water, to form an 8% solution by weight. This solution is applied to a rayon fabric using the procedure of Example 5. The resulting product is permanently water repellent.

Example 13 l,1,3,3 tetramethyl 1,3,di 2 chloroethoxydisiloxane is prepared by adding 200 cc. of cold water to a cold mixture of 2 moles of dimethyl- 2-chloroethoxychlorosilane and 1.3 moles of pyridine. The two layers which form are separated, and the upper layer washed several times with 15% sodium hydroxide solution and then dried over calcium chloride. Unreacted silane is removed by fractional distillation. in vacuum.

The disilicate is then added in small portions to an excess of pyridine and the resulting mixture warmed at 60 C. until separation of the pyridinium chloride, which has the formula:

This compound is dissolved in a solution containing equal weights of water and pyridine to form a 5% solution. A rayon fabric is padded with this solution to pick-up by weight. It is then dried at 60 C. and cured at C. for 3 minutes. The cured fabric is rinsed and then immersed in 1% aqueous sodium hydroxide solution for one hour at 60 C. It is then warmed in an oven at 60 C. in a humid atmosphere, dried and cured at C. for 15 minutes. The resulting product is water repellent and shows improved shrink resistance.

Errample 14 One part of trimethyl(ethoxy pyridinium chloride) silane and two parts of dimethyl di(ethoxy pyridinium chloride) silane are dissolved in water, to form an eight per cent solution. The pH of this solution is adjusted to 9 by addition of triethanolamine. This solution is padded at room temperature on a cotton-rayon fabric to a 100% pick-up by weight. The fabric is heated in an oven at 100 C. in steam of a humid atmos here for one-half hour, dried and then baked at 150 C. for 15 minutes and rinsed. The treated fabric is dimensionally stable and water repellent.

Example 15 Equal parts of methyltriethoxy pyridinium chloride silane and dimethyldiethoxy pyridinium chloride silane, together with an equal weight of pyridine, are dissolved in water to form a ten per cent solution. The pH of the solution is adjusted to 8.5 by addition of a small amount of triethanolamine. A rayon fabric is padded with the solution at room temperature to a 100% pickup by weight. The treated fabric is then warmed at 80 C. for one hour in a moist atmosphere, dried, and baked at 120 C. for one hour and at for three minutes, rinsed and dried. It then exhibits good water repellency and crease resistance.

Example 16 A mixture of methy1 tri(propoxypyridiniumchloride) silane and trimethyl propoXy p ridinium chloride silane, prepared according to the procedure set forth in Example 1, is dissolved in water in the presence of an equal Weight of pyridine to form a six per cent solution. A rayon fabric is padded with the solution to 100% pickup by weight. The treated fabric is warmed at 70 C. for one hour and then at 85 C. for one hour in a humid atmosphere, and then cured at 140 C for 35 minutes. The cured fabric is rinsed and dried. It exhibits permanent water repellency, crease resistance, and dimensional stability.

Example 17 Trimethyl(ethoxytributyl quaternary ammonium chloride) silane is dissolved in water to form an eight per cent solution whose pH is adjusted to 9 by addition of triethanolamine. A cotton fabric is added with this solution to a 100% pick-up by weight. The fabric is warmed in a 19 humid atmosphere at 60 C. for one and one-half hours, dried, and then baked at 150 C. for 15 minutes, washed with soap solution and rinsed. The resulting product is permanently waterrepellent.

Example 18 Octadecyldimethyl(ethoxy pyridinium chloride) silane is dissolved in water to form a 10% solution. A rayon fabric is padded with this solution to a 100% pick-up by weight, dried at 70 C. and then baked at 140 C. for minutes, washed with aqueous sodium bicarbonate solution, rinsed and dried. The cured fabric is then permanently Water repellent.

Example 19 Trimethyl(oxystearamidomethyl pyridinium chloride) silane is dissolved in water to form an 8% solution by weight. Wool and cotton fabrics are padded with this solution to 100% pick-up, dried at 50 C. and then baked at 110 C. for minutes, washed with soap solution, rinsed and dried. The resulting products are permanently water repellent.

The following is claimed:

1. Compounds having the general formula:

where n is an integer from 1 to 3; R is selected from the group consisting of saturated alkyl hydrocarbon radicals, alicyclic hydrocarbon radicals and aryl hydrocarbon radicals havingfrom 1 to about carbon atoms; Y is a bivalent bridging radical selected from the group consisting of alkylene arylene and cycloalkylene hydrocarbon radicals having from 1 to about carbon atoms; N(tert) is a tertiary amine selected from the group consisting of tertiary aliphatic amines and tertiary heterocyclic amines; and X is a chlorine atom.

2. Compounds having the formula msqownomoansoni-.. where n is an integer from 1 to 3, R is an alkyl hydrocarbon radical having less than 20 carbon atoms, and y is an integer from 1 to 30.

3. Trimethyl(ethoxy pyridinium chloride) silane.

4. A process of treating organic textile materials to modify the physical characteristics thereof which comprises impregnating said material with from about 0.1 per cent to 20 per cent by weight of said material of a compound of claim 1 in aqueous solution, drying said material at a temperature of less than about 100 C., and heating said material to a temperature of from to 260 C. to decompose the quaternary ammonium compound while leaving the siloxy linkage intact and to bond the reaction products to the material.

5. A process of treating organic textile material to modify the physical characteristics thereof which comprises impregnating said material with from about 0.1 per cent to 20 per cent by weight of said material of a compound of claim 1 in aqueous solution, drying said material at a temperature of less than about 0., heating said material to a temperature of from 80 to 260 C. to decompose the quaternary ammonium compound, then hydrolyzing the siliconoxygen linkage of said compound, warming said material at a temperature of from about 40 to C. and, finally, heating said material to a temperature of from 80 to 250 C. to bond the reaction products to said material.

6. A process of treating organic textile material to modify the physical characteristics thereof which comprises impregnating said material with from about 0.1 per cent to 20 per cent by weight of said material of a compound of claim 1 in aqueous solution, hydrolyzing the silicon-oxygen linkage of said compound, Warming said material at a temperature of from 40 to 80 0., drying said material at a temperature of less than 100 C. and, finally, heating said material at a temperature of from 80 to 250 C. to bond the reaction products thereto.

7. The process as in claim 6 wherein the solution with which said material is impregnated has a pH of from about 5 to 10 whereby said hydrolysis is effected concurrently with said impregnating step.

JOHN ROBERT JANES.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,258,218 Rochow Oct. 7, 1941 2,277,174 Krefeld Mar. 24, 1942 2,415,017 MacKenzie Jan. 28. 1947 2,462,635 Haber Feb. 22, 1949 OTHER REFERENCES Dearing et al.: Journal American Chemical Society, volume 50 (1928), pages 3058 to 3062. 

1. COMPOUNDS HAVING THE GENERAL FORMULA:
 5. A PROCESS OF TREATING ORGANIC TEXTILE MATERIAL TO MODIFY THE PHYSICAL CHARACTERISTICS THEREOF WHICH COMPRISES IMPREGNATING SAID MATERIAL WITH FROM ABOUT 0.1 PER CENT TO 20 PER CENT BY WEIGHT OF SAID MATERIAL OF A COMPOUND OF CLAIM 1 IN AQUEOUS SOLUTION, DRYING SAID MATERIAL AT A TEMPERATURE OF LESS THAN ABOUT 100* C. HEATING SAID MATERIAL TO A TEMPERATURE OF FROM 80* TO 260* C. TO DECOMPOSE THE QUATERNARY AMMONIUM COMPOUND, THEN HYDROLYZING THE SILICONOXYGEN LINKAGE OF SAID COMPOUND, WARMING SAID MATERIAL AT A TEMPERATURE OF FROM ABOUT 40* TO 150* C. AND, FINALLY, HEATING SAID MATERIAL TO A TEMPERATURE OF FROM 80* TO 250* C. TO BOND THE REACTION PRODUCTS TO SAID MATERIAL. 